EP3229988B1 - Procédé de fabrication d'électrode feuilles pour condensateurs, des feuilles d'électrode et condensateurs avec les feuilles de électrode - Google Patents

Procédé de fabrication d'électrode feuilles pour condensateurs, des feuilles d'électrode et condensateurs avec les feuilles de électrode Download PDF

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EP3229988B1
EP3229988B1 EP15805201.9A EP15805201A EP3229988B1 EP 3229988 B1 EP3229988 B1 EP 3229988B1 EP 15805201 A EP15805201 A EP 15805201A EP 3229988 B1 EP3229988 B1 EP 3229988B1
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Prior art keywords
metal foil
microstructures
electrode
foil
metal
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German (de)
English (en)
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EP3229988A1 (fr
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Erkan KUZECI
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TDK Electronics AG
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TDK Electronics AG
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D33/00—Special measures in connection with working metal foils, e.g. gold foils
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029—Processes of manufacture
    • H01G9/0032—Processes of manufacture formation of the dielectric layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/055—Etched foil electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/07—Dielectric layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/145—Liquid electrolytic capacitors

Definitions

  • Electrode foils for capacitors must have the largest possible surface area in order to increase the capacitance of the capacitors.
  • the market request tends to electrolytic capacitors with increasingly higher voltages (up to 1200 V f ).
  • the metal foils as electrodes must also have a high mechanical resistance in order to withstand the high speeds of the winding machine during the manufacture of the capacitors.
  • metal foils which may for example consist of a valve metal, such as aluminum, are treated by means of an electrochemical etching process in such a way that the surface area is increased.
  • This method has the disadvantage that the metal foils can lose up to 30% in weight during the etching process, so that their mechanical resistance is reduced in comparison to unetched foils.
  • the electrochemical etching process leads to a high consumption of acids and requires large amounts of liquid, acidic waste.
  • the etching process leads to irregular structures and channels on the surface of the metal foils.
  • High-purity metal foils which have a purity of> 99%, for example aluminum foils, which have on their surface a high crystalline texture, in particular a high cubic texture ( ⁇ 100 ⁇ ⁇ 001>), are frequently used in order to allow a controlled etching of the metal foils. respectively.
  • This cubic texture is important because etching preferably takes place along the crystallographic ⁇ 001> direction.
  • the production of metal foils with high crystalline, in particular cubic texture is very time consuming and costly and requires complex rolling steps at different temperatures, which can last lead by an annealing process to form a largely cubic texture.
  • An object of the present invention is to provide a process for producing electrode films for capacitors, which is improved in terms of the above-mentioned disadvantages. Further aspects of the present invention are directed to improved electrode films for capacitors as well as to capacitors having these electrode films.
  • Forming is understood here to be any method in which the metal foil is plastically brought into another shape.
  • forming also refers to an embossing process in which by means of pressure located on a stamp Microstructures are transferred to a main surface of the metal foil.
  • embossing for example, the stamp can be pressed against the main surface of the metal foil or conversely, the metal foil, for example, pressed together with a substrate supporting the foil against the stamp. It is also possible a relative movement of the punch and the metal foil toward each other during the forming process.
  • the transfer of the microstructures from the stamp to the main surface of the metal foil by forming does not result in any waste, in particular no liquid waste.
  • Another advantage is that, in contrast to the etching process, the metal foil loses no substance and thus can be mechanically more stable compared to etched metal foils.
  • microstructures transferred by means of the forming process are in particular structures on the surface of the metal foil, for example recesses and elevations. These microstructures particularly advantageously cause an increase in the specific surface of the metal foil, so that capacitors having these metal foils as electrodes have an increased capacitance.
  • a metal foil be used comprising or consisting of a valve metal.
  • Valve metals in which an oxide layer of the metal can be produced on the metal foil by means of electrochemical processes, for example anodic oxidation, are particularly suitable as electrodes for capacitors, since the oxide layer of the metal acts as a dielectric.
  • the oxide layer causes the dielectric strength of the capacitor, wherein in particular with the thickness of the oxide layer, the rated voltage of the capacitor can be set very easily.
  • valve metals on which an oxide layer of the metal can be produced by electrochemical methods for example, aluminum, tantalum, niobium, manganese, titanium, bismuth, antimony, zinc, cadmium, zirconium, tungsten, tin, iron, silver and silicon are preferable Aluminum, tantalum and niobium and most preferably aluminum.
  • Aluminum is particularly preferred as valve metal, since aluminum metal foils can be used particularly well as electrodes for electrolytic capacitors, in particular aluminum electrolytic capacitors.
  • a metal oxide layer can be produced on the metal foil as a dielectric. This can, as already described above, be carried out by means of electrochemical processes, in particular anodic oxidation, when metal foils be used comprising or consisting of a valve metal.
  • metal foils which are produced by the method according to the invention, can be used on these metal foils z. B. for high-voltage applications with up to 20 times increased surface area compared to the unshaped films particularly simple stable oxide layers are produced as a dielectric.
  • the metal foil can be positioned between two punches and thus the microstructures located on both punches can be transferred to the two main surfaces of the metal foil by forming, for example pressing.
  • both main surfaces of the metal foil can be particularly easily provided by embossing with a raised surface and with microstructures.
  • this method may be formed as a continuous process, wherein in step B) the metal foil is passed between two rotating rollers as a stamp and thereby the microstructures at least one or both main surfaces of the metal foil are transferred.
  • the stamp by means of which the metal foils are embossed, can also be produced by the LIGA process.
  • LIGA stands for lithography, electroforming, and impression taking. This method can be used to produce on stamps microstructures also in a three-dimensional arrangement with a high aspect ratio.
  • a photosensitive monomer typically an acrylate-based
  • This monomer layer is then irradiated with high-energy rays, for example X-rays or UV rays, through a mask defining the microstructures to be obtained, the irradiated regions of the monomer layer polymerizing, while the monomers are still present in the non-irradiated regions ( negative resist).
  • the unpolymerized monomers can then be removed by means of a chemical developer solution so that a polymer layer provided with the microstructures remains on the electrically conductive substrate.
  • metals such as cobalt or nickel may then be introduced into the empty voids of the polymerized layer.
  • the structured polymer is then removed to leave a patterned metal layer which can be used as a stamp for the methods of the invention.
  • LIGA the publication EW Becker, W. Ehrfeld, P. Hagmann, A. Mana, D. Münchmeier: "Fabrication of Microstructures with High Aspect Ratios and Great Structural Heights” by Synchrotron Radiation Lithography, Galvanoforming, and Plastic Molding (LIGA Process); ", Number 1, 1986, pages 35-56 Referenced.
  • this LIGA method makes it possible to produce metal structures with a height of a few 100 ⁇ m, which have deviations of less than 0.1 ⁇ m in the dimensions.
  • metals for the dies for use in the process according to the invention cobalt, nickel, copper as well as nickel / iron alloys can be used.
  • the photoresist SU-8 which has as the monomer component an epoxy resin having the following structure with a total of eight epoxy groups in the molecule:
  • This monomer can be dissolved in a solvent, for example ⁇ -butyrolactone or cyclopentanone, using as its photosensitive component a photoacid which liberates an acid upon irradiation with, for example, UV light at a wavelength of 365 nm.
  • This acid may be, for example, triarylsulfonium hexafluoroantimonate, which initiates polymerization in the epoxy resin when exposed to radiation.
  • 1-methoxy-2-propanol acetate can be used as the developer.
  • the microstructures can form structures with a defined depth or elevation in the surface, wherein also defined distances are present between individual microstructures on the surface of the metal foil.
  • the elevations or depressions in the surface for the microstructures and also the distances from adjacent microstructures to one another can vary by a maximum of 15%, preferably by a maximum of less than 10% and preferably by a maximum of less than 5%.
  • the deviations can be only in the order of 0.1 microns.
  • regular microstructures can be produced particularly easily by forming processes, such as embossing, in the metal foils and thus allow a particularly defined method to increase the surfaces of the electrode foils in a targeted manner, without posing the risk of breakthroughs in the metal foil. This is a great advantage compared to the chemical etching method conventionally used.
  • the microstructures also include a plurality of depressions in the metal foil. These recesses can take on either oval, round or polygonal shapes in the plan view of the main surface of the metal foil. In cross-section, the recesses may in particular also have widths which form the interior of the metal foil rejuvenate or remain approximately the same (see also the FIGS. 2a and 4b ).
  • microstructures are produced on the surface of the metal foil which comprise trenches, wherein the trenches are arranged at defined distances from one another.
  • the depth of the trenches is 20 ⁇ m or more and the width of the trenches is at most 5 ⁇ m.
  • the trenches can also have distances from each other, which are at most 5 microns.
  • microstructures produced may also comprise microstructures of different shapes, for example a combination of trenches and depressions.
  • microstructures having the largest possible aspect ratios, ie, the smallest possible size, on at least one main surface of the metal foil in order to achieve the largest possible surface area of the electrode foils and thus an improved capacitance of the capacitors equipped with the electrode foils.
  • the elevations of the microstructures may also have small connecting webs between adjacent microstructures, for example to increase their mechanical stability.
  • the height or the depressions of the microstructures and their distances from one another can be determined particularly simply by means of scanning electron microscopy familiar to a person skilled in the art.
  • the dies in process step B), in particular can be used at a temperature below 600 ° C., 500 ° C. or 400 ° C., below 320 ° C., preferably below 200 ° C., more preferably ⁇ 100 ° C. pressed the metal foil, wherein the temperature can also be room temperature.
  • the temperature can also be room temperature.
  • metal foils are not thermoplastic, the inventors have found that especially at temperatures of ⁇ 400 ° C no alloying effects between the metal foil and the metallic stamp, such as a nickel stamp , occur.
  • the punches and the metal foil can be pressed against each other in a very wide pressure range as a function of the temperature and of the embossing device.
  • embossing the metal foils works particularly well at pressures in the range of 10 to 100 MPa.
  • a metal foil having a crystalline, ie in particular cubic texture of ⁇ 90%, preferably ⁇ 50%, more preferably without cubic texture is provided.
  • metal foils in particular aluminum foils
  • a high cubic Texture can be used, along which can be preferably etched.
  • metal foils which are not subjected to elaborate rolling processes at different temperatures and annealing procedures to produce a high crystalline texture on the surface. Therefore, cheaper to produce films can be used in the inventive method. In principle, however, films with a high cubic texture can be used.
  • the process of the invention can work better.
  • even the smallest inclination angles of the cubic texture surface of the metal foils lead to different etch results, while these inclinations of the cubic texture surface do not play a major role in the forming processes of the present invention.
  • the crystalline, in particular cubic texture of surfaces of metal foils can, for. B. by scanning electron microscopy in conjunction with Electron Backscatter Diffraction (EBSD) can be determined. These methods can be carried out with scanning electron microscopes or transmission electron microscopes and allow the spatially resolved determination of the crystal symmetries of the surface of the metal foils.
  • EBSD Electron Backscatter Diffraction
  • a metal foil having a purity of> 95%, preferably> 98%, can be provided, it also being possible for the purities to reach very high values of up to 99.9% to 99.99%.
  • metal foils with a thickness of at least 120 ⁇ m, preferably at least 100 ⁇ m, most preferably at least 80 ⁇ m, can be provided.
  • the inventors have found that, with such minimum thicknesses, particularly economical results are achieved in the case of forming processes according to the invention.
  • the present invention also relates to electrode films which have been produced according to the inventive method, and thus in particular also comprise a metal foil having regular microstructures on at least one main surface.
  • These microstructures are, as already described, embossed microstructures and in particular have defined depths or elevations as well as defined distances between individual adjacent microstructures.
  • the variation of the heights or the depressions of the microstructures and their distances from each other can vary by a maximum of 20%, preferably 15%, more preferably 5%. Also possible are deviations in the range of 0.1 ⁇ m.
  • Embodiments of the electrode films of the invention may have a thickness of less than 100 microns, preferably up to 88 microns and, when used in aluminum electrolytic capacitors as electrode foil a capacity of about 0, 2 microfarads / cm2 at 900 volts formation.
  • the metal foil comprises a valve metal, in particular the abovementioned metals, preferably aluminum, tantalum or niobium.
  • Aluminum metal foils are particularly preferred for use in aluminum electrolytic capacitors.
  • the microstructures include trenches having an aspect ratio of at least 4: 1.
  • the depth of the trenches are at least 20 microns and their width at most 5 microns and the distance between individual trenches can be at most 5 microns.
  • the metal foil may have a crystalline, in particular cubic, texture of ⁇ 90%, preferably ⁇ 80%, or even completely lacking in texture, since a crystalline surface texture is not necessarily needed for a mechanical forming process.
  • a metal oxide layer as a dielectric for example by means of anodic oxidation, can be produced over the microstructures.
  • This is particularly simple in the case of aluminum electrode films, for example, by a so-called forming process possible, which can be divided into four process steps in principle.
  • aluminum hydroxides are formed by reaction in an aqueous medium, e.g. B. formed a hot water. This forms a complex aluminum hydroxide, the so-called boehmite layer.
  • This process step is followed by an anodic oxidation of the film in neutral electrolytes, which converts the boehmite layer to gamma-aluminum and directly produces another oxide layer by oxidation of metallic aluminum. Since the conversion of metallic aluminum into alumina at the same time causes a change in the density of the material (density of aluminum 2.7 g / m 3 , density of alumina 3.8 g / cm 3 ) are also cracks and cavities in the process step Inside the oxide layer generated.
  • these defects are first wetted with an electrolyte (so-called depolarization step) and then, by means of an anodic polarization, the final fourth forming step, these defects are healed.
  • the thickness of the oxide layer formed during the formation may increase, with the increase taking place in a ratio of 1 nm / 1 volt.
  • a forming voltage of 560 V may then result in a thickness of the oxide layer of approximately 0.56 ⁇ m.
  • a significant advantage of the method according to the invention is that the structures for different voltages d. H. different oxide layer thicknesses are tailor-made dimensioned so that the growing oxide layers can not lead to a decrease in the specific surface area.
  • FIG. 1a shows in cross-section an embossed by means of a forming process according to the invention electrode film 1, wherein on both main surfaces 1a, 1b, the microstructures 2 were generated. It can be seen that trenches 2 were formed on both main surfaces, wherein the width of the trenches 2b is similar to the distance 2a of two adjacent trenches to each other. The width of the trenches 2b and the distance 2a of two adjacent trenches may also have different dimensions, wherein the walls of the channels need not necessarily be perpendicular to the film plane, but may also have a different angle to the film plane.
  • FIG. 1a can also be found that the thickness of the metal foil is greater than the depth of the microstructures, so that in the cross section of the film in the interior 1c of the film, an unembossed region 1c without microstructures is present, which gives the film a high mechanical stability.
  • FIG. 1b shows a perspective view of the course of the trenches to each other. Both FIGS. 1a and 1b it can be seen that the width of the trenches remains approximately the same towards the interior of the electrode foil.
  • Figure 1C schematically shows how the microstructures 2 are transferred to the electrode film 1 by means of a roller as a stamp 3.
  • FIG. 2a shows typical scanning electron micrographs of the trenches 2 of a 120 micron thick aluminum electrode foil both in the top view and in perspective view.
  • webs 2d can also run between individual trenches, which can in particular provide for an increase in the mechanical stability of the microstructures.
  • the depth of the trenches is 20 ⁇ m and the width is 5 ⁇ m.
  • the spacing of adjacent trenches is also approximately on the order of 5 microns.
  • FIG. 2b shows in contrast to FIG. 2a Tunnel 2e, which can be formed by means of a Vortician suitss in the context of conventional etching in aluminum electrode films. Clearly visible is the irregular arrangement of the tunnels 2e, which in clear contrast to the regular, defined microstructures of the embossed films in the FIG. 2a stands.
  • a piece of aluminum foil 1 having a thickness greater than the height of the structures to be produced may be positioned on a so-called substrate plate 3b, the dimensions of the metal foil 1 being approximately correspond to the dimensions of the substrate plate 3b.
  • both the substrate plate and also the stamp 3a, in which the microstructures to be transferred are present can be heated to the embossing temperature, for example a temperature of ⁇ 320 ° C.
  • the embossing begins, wherein at a constant embossing rate of the punch 3a and the substrate plate 3b are moved against each other until the preset maximum embossing force is reached.
  • the relative movement between the punch 3a and the substrate plate 3b is determined by this constant stamping force.
  • the metal foil 1 flows under the constant pressure. Due to this flow, the thickness of the metal foil decreases with increasing time of remaining in the embossing device.
  • the temperature is kept constant.
  • the embossed metal foil is removed from the mold by a relative movement between the substrate plate and the embossed metal foil.
  • the adhesion of the residual layer of the metal foil to the substrate plate plays an important role.
  • Residual layer is understood to be the thickness of the metal foil which is present after the deformation. Higher adhesion of the remaining layer on the substrate plate ensures that the microstructures can be removed from the mold in the vertical direction, which reduces the risk of damage.
  • Demoulding is the most critical process step of hot stamping. Demolding is particularly important in reducing the structure size of microstructures due to the increasing influence of shrinkage of the material.
  • Shrinkage can take place in particular in the size range of the structure size of the microstructures and therefore increases the risk of damage to free-standing microstructures.
  • the effect of shrinkage is also a function of the process parameters during the stamping process, especially the stamping force and the stamping temperature.
  • F the embossing force
  • ⁇ the viscosity of the material
  • R the diameter of the plate
  • h 0 the thickness of the material to be embossed
  • dz dt represents the forming speed, the speed at which the material of the metal foil flows into the cavities or microstructures of the stamp. Due to these relationships, it is clear that the embossing force increases with decreasing thickness as well as with increasing area of the material to be embossed.
  • a roll-to-roll production process as a continuous process is very economical in which the electrode films, the metal foils are passed between two rotating rollers under pressure and possibly with heating to an embossing temperature, so that a continuous Embossing process can be performed.
  • z. B. realize anodic films in which, for example, a central film is flanked by two other films on the respective main surfaces. Through the holes through all layers of the films can be wetted with the electrolyte.
  • Such a continuous roll-to-roll process is schematically in cross-section in FIG. 4a shown, with two Rollers 3 with microstructures 2 rotate against each other and a metal foil 1 is passed under pressure, wherein the structures 2 are particularly easily generated on the metal foil as an electrode foil.
  • the arrows indicate schematically the rotation of the roller dies and the movement of the metal foil 1.
  • FIG. 4b shows scanning electron micrographs of regular microstructures in aluminum electrode foils with a thickness of 120 ⁇ m in the top view (left picture) and in the cross section (right picture).
  • regular trenches regular recesses are here generated with a square cross-section in the plan view of the main surface of the metal foil, with the cross sections of the microstructures tapering towards the interior of the electrode film.
  • FIG. 5 shows schematically in cross section a capacitor, for example an aluminum electrolytic capacitor, in which an electrode film 1 according to the invention is used.
  • This electrode film 1 has the already described microstructures 2 as regular trenches and an oxide layer 5 applied thereto as a dielectric.
  • the electrode foil 1 can be used, for example, as an anode foil.
  • a further metal foil 4 is provided which can serve as a current collector.
  • a spacer 7 may be present between this further metal foil 4 and the electrode foil 1, for example a plastic foil or a paper foil which has been impregnated with an electrolyte 6.
  • the electrolyte can act together with the further electrode film 4 as a current collector as a counter electrode to the electrode film 1, ie in particular as a cathode. It can be the more Electrode film 4 designed differently than the electrode film 1 or also be constructed the same.
  • the further electrode foil 4 can also be an aluminum foil with a high surface area, but the forming layer does not have to be present.
  • Electrolytic capacitors Due to the increased regular surface of the electrode foil 1, such electrolytic capacitors have increased capacity and increased stability. With the existing technology using Al 2 O 3 as the metal oxide layer (dielectric), it is possible to achieve capacitance values of> 0.2 ⁇ F / cm 2 at 900 volts for metal foils, in particular aluminum foils, the thickness of the metal foils being ⁇ 80 ⁇ m.
  • such electrolytic capacitors can be realized particularly simply as electrode windings in which the electrode film is unwound from rolls and subjected to higher mechanical stress. Due to their increased mechanical stability, electrode foils according to the invention can be exposed to this roll-to-roll production process without mechanical damage being expected. As an alternative to this roll-to-roll production method, the electrode foils according to the invention can also be used with preference for capacitors which are produced by stacking electrode foils one above the other.
  • electrolyte solutions for the electrolytic capacitors in particular aluminum electrolytic capacitors, it is possible to use any conventional electrolytic solutions, for example electrolytic solutions which contain ethylene glycol as the solvent and ammonium pentaborate NH 4 B 5 O 8 as the conductive salt. These electrolyte solutions may have more Contain additives. Alternatively, it is also possible to use electrolyte solutions which at least partly contain water as solvent. Electrode foils according to the invention can also be used in capacitors which comprise, as electrolytes, anhydrous ionic liquids or else particularly preferably solids.

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  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
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Claims (17)

  1. Procédé de fabrication de feuilles d'électrodes (1) pour condensateurs (10), comprenant les étapes de procédé suivantes :
    A) fourniture d'une feuille de métal (1),
    B) transfert par formage de microstructures (2) présentes sur un poinçon (3, 3a) à une surface principale de la feuille de métal, par une étape de procédé faisant suite à l'étape de procédé B),
    C) créer une couche d'oxyde métallique (5) sur la feuille de métal (1),
    dans lequel
    - les feuilles d'électrodes (1) ne sont pas percées,
    - lors de l'étape de procédé B), les microstructures (2) sont créées de manière à comporter des tranchées présentant un rapport de forme d'au moins 4:1, et
    - lors de l'étape de procédé B), les tranchées sont réalisées de manière à présenter une profondeur d'au moins 20 µm et une largeur d'au plus 5 µm.
  2. Procédé de fabrication de feuilles d'électrodes (1) pour condensateurs (10) selon la revendication précédente, dans lequel, lors de l'étape de procédé A), une feuille de métal comprenant ou consistant en un métal de soupape est utilisée.
  3. Procédé selon l'une des revendications précédentes, dans lequel, lors de l'étape de procédé B), la feuille de métal (1a) est positionnée entre deux poinçons (3) et les microstructures (2) présentes sur les deux poinçons sont transférées par pressage sur les surfaces principales de la feuille de métal.
  4. Procédé de fabrication de feuilles d'électrodes (1) pour condensateurs (10) selon l'une des revendications précédentes, mis en oeuvre sous la forme d'un procédé en continu, dans lequel, lors de l'étape de procédé B), la feuille de métal (1a) est amenée à passer entre deux rouleaux rotatifs en tant que poinçon (3) et les microstructures (2) sont ainsi transférées sur au moins une surface principale de la feuille de métal.
  5. Procédé selon l'une des revendications précédentes, dans lequel des microstructures régulières sont créées lors de l'étape de procédé B).
  6. Procédé selon l'une des revendications précédentes, dans lequel, lors de l'étape de procédé B), les poinçons sont pressés contre la feuille de métal à une température inférieure à 400°C, de préférence inférieure à 200°C, et plus préférablement inférieure à 100°C, dans lequel la température peut également être la température ambiante.
  7. Procédé selon l'une des revendications précédentes, dans lequel, lors de l'étape de procédé B), les poinçons et la feuille de métal sont pressés l'un contre l'autre sous une pression pouvant atteindre 100 MPa.
  8. Procédé selon l'une des revendications précédentes, dans lequel, lors de l'étape de procédé A), on fournit une feuille de métal ayant une texture cristalline, par exemple cubique, de < 90%, de préférence < 50%, et plus préférablement sans texture.
  9. Procédé selon l'une des revendications précédentes, dans lequel, lors de l'étape de procédé A), on fournit une feuille de métal ayant une pureté de > 95 %, de préférence > 98 %.
  10. Procédé selon l'une des revendications précédentes, dans lequel, lors de l'étape de procédé A), on fournit une feuille de métal ayant une épaisseur d'au moins 120 µm, de préférence d'au moins 100 µm, et plus préférablement, d'au moins 80 µm.
  11. Procédé selon l'une des revendications précédentes, dans lequel, lors de l'étape de procédé B), des microstructures (2) sont transférées sous la forme d'une pluralité de creux sur la surface principale de la feuille de métal.
  12. Feuille d'électrode pour condensateurs, comprenant :
    - une feuille de métal sans orifices traversants comportant une couche d'oxyde métallique et des microstructures régulières sur au moins une surface principale,
    dans laquelle
    - les microstructures (2) comportent des tranchées présentant un rapport de forme d'au moins 4:1,
    - les tranchées présentent une profondeur d'au moins 20 µm et une largeur d'au plus 5 µm.
  13. Feuille d'électrode pour condensateurs selon la revendication précédente du brevet, dans laquelle la feuille de métal comprend ou consiste en un métal de soupape.
  14. Feuille d'électrode selon l'une des revendications 12 à 13, dans laquelle la feuille de métal présente une texture cristalline (cubique) de < 90%, de préférence < 80%, et plus préférablement sans texture.
  15. Feuille d'électrode selon l'une des revendications 12 à 14, dans laquelle une couche d'oxyde métallique est disposée sur les microstructures.
  16. Feuille d'électrode selon l'une des revendications 12 à 15, dans laquelle les microstructures sont présentes sous la forme d'une pluralité de creux.
  17. Condensateur électrolytique (10) comprenant :
    - une feuille d'électrode selon l'une des revendications 12 à 16 en tant que première électrode (1),
    - une autre feuille de métal (4) en tant que collecteur de courant pour une seconde électrode et
    - une solution d'électrolyte (6) disposée entre la première électrode et le collecteur de courant de la seconde électrode.
EP15805201.9A 2014-12-09 2015-12-07 Procédé de fabrication d'électrode feuilles pour condensateurs, des feuilles d'électrode et condensateurs avec les feuilles de électrode Active EP3229988B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014118222.7A DE102014118222A1 (de) 2014-12-09 2014-12-09 Verfahren zur Herstellung von Elektrodenfolien für Kondensatoren, Elektrodenfolien und Kondensatoren mit den Elektrodenfolien
PCT/EP2015/078868 WO2016091824A1 (fr) 2014-12-09 2015-12-07 Procédé de fabrication d'électrodes en feuille pour des condensateurs, électrodes en feuille et condensateurs pourvus desdites électrodes

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WO (1) WO2016091824A1 (fr)

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DE102019123877B4 (de) * 2019-09-05 2022-06-09 CRRC New Material Technologies GmbH Dielektrische Vorrichtung mit einer Elektrode mit nicht-planaren Strukturierungen

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Publication number Publication date
EP3229988A1 (fr) 2017-10-18
DE102014118222A1 (de) 2016-06-23
US20170271086A1 (en) 2017-09-21
US10354807B2 (en) 2019-07-16
WO2016091824A1 (fr) 2016-06-16
JP2017539092A (ja) 2017-12-28

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